Mechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation
Title | Mechanistically guided one pot synthesis of phosphine-phosphite and its implication in asymmetric hydrogenation |
Publication Type | Journal Article |
Year of Publication | 2022 |
Authors | Sen, A, Kumar, R, Pandey, S, K. Raj, V, Kumar, P, Vanka, K, Chikkali, SH |
Journal | European Journal of Organic Chemistry |
Volume | 2022 |
Issue | 2 |
Pagination | e202101447 |
Date Published | JAN |
Type of Article | Article |
ISSN | 1434-193X |
Keywords | asymmetric hydrogenation, catalysis, DOPA synthesis, One pot synthesis, Phosphine-phosphite ligand |
Abstract | Although hybrid bidentate ligands are known to yield highly enantioselective products in asymmetric hydrogenation (AH), synthesis of these ligands is an arduous process. Herein, a one pot, atom-economic synthesis of a hybrid phosphine-phosphite (L1) is reported. After understanding the reactivity difference between an 0-nucleophile versus C-nucleophile, one pot synthesis of Senphos (L1) was achieved (72%). When L1 was treated with [Rh], P-31 NMR revealed bidentate coordination to Rh. Senphos, in the presence of rhodium, catalyzes the AH of Methyl-2-acetamido-3-phenylacrylate and discloses an unprecedented turn over frequency of 2289, along with excellent enantio-selectivity (92%). The generality is demonstrated by hydrogenating an array of alkenes. The AH operates under mild conditions of 1-2 bar H-2 pressure, at room temperature. The practical relevance of Ll is demonstrated by scaling-up the reaction to 1 g and by synthesizing DOPA, a drug widely employed for the treatment of Parkinson's disease. Computational insights indicate that the R isomer is preferred by 3.8 kcal/mol over the S isomer. |
DOI | 10.1002/ejoc.202101447 |
Type of Journal (Indian or Foreign) | Foreign |
Impact Factor (IF) | 3.021 |
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